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Carboranes are boron-carbon clusters with important applications in the fields of materials, catalysis, pharmaceuticals, etc. However, the noncovalent interactions that could determine the solid-state structures and properties of such boron clusters have rarely been investigated. Herein, inspired by the coordinate bond in metallacarborane or ferrocene, the boron cluster-based noncovalent interaction (denoted as cage - ···cage - interaction) between two nido -carborane clusters was successfully realized by using a pyridinium-based molecular barrier. The X-ray diffraction studies uncover that the cage - ···cage - interaction has a contacting distance of 5.4-7.0 Å from centroid to centroid in the systems reported here. Theoretical calculations validate the formation of the noncovalent interaction and disclose its repulsive bonding nature that is overcome thanks to the positively charged pyridinium-based framework. Interestingly, such bulk crystalline materials containing the cage - ···cage - interaction show relevant properties such as full-color absorption in the visible light range and important photothermal effect, which are absent for the control compound without carboranes. This study may offer fundamental insights into the boron cluster-based noncovalent interactions and open a new research avenue to rationally design boron cluster-based materials.

Cage–···Cage– Interaction: Boron Cluster-Based Noncovalent Bond and Its Applications in Solid-State Materials

Cage^–···Cage^– Interaction: Boron Cluster-Based Noncovalent Bond and Its Applications in Solid-State Materials